Lithium-metal batteries having improved dimensional stability and methods of manufacture

ABSTRACT

Lithium-metal batteries with improved dimensional stability are presented along with methods of manufacture. The lithium-metal batteries incorporate an anode cell that reduces dimensional changes during charging and discharging. The anode cell includes a container having a first portion and a second portion to form an enclosed cavity. The first portion is electrically-conductive and chemically-stable to lithium metal. The second portion is permeable to lithium ions and chemically-stable to lithium metal. The anode cell also includes an anode comprising lithium metal and disposed within the cavity. The anode is in contact with the first portion and the second portion. The cavity is configured such that volumetric expansion and contraction of the anode during charging and discharging is accommodated entirely therein.

CROSS-REFERENCE TO RELATED APPLICATION(S)

The present application claims the benefit under 35 U.S.C. § 119(e) ofU.S. Provisional Appl. No. 62/300,279, entitled “Lithium-Metal BatteriesHaving Improved Dimensional Stability and Methods of Manufacture,” filedon Feb. 26, 2016, which is incorporated herein by reference in itsentirety.

FIELD

This disclosure relates generally to lithium-metal batteries, and moreparticularly, to anode cells that allow for improved dimensionalstability of lithium-metal batteries.

BACKGROUND

During operation, lithium-metal batteries often undergo cyclingprocesses, which include charging and discharging. During charging, ananode of a lithium-metal battery is continuously plated with lithiummetal. During discharging, the anode is continuously stripped of lithiummetal. The anode experiences volumetric expansion and contraction inresponse to, respectively, plating and stripping of lithium metal. Suchvolumetric expansion and contraction produces undesirable dimensionalchanges within an anode cell. These dimensional changes are typicallyconcomitant with material stresses, which may reduce the performance ofthe lithium-metal battery or cause premature failure.

Lithium-metal batteries may sometimes be arranged in a stacked sequence.In the stacked sequence, however, volumetric expansion and contractionoccurs cumulatively: each lithium-metal battery contributes in additivefashion to a larger, effective dimensional change. This larger,effective dimensional change typically requires void space to bereserved within a target application (e.g., a battery package or abattery-powered apparatus). Reserved void space represents anundesirable loss of functional volume within the target application.

The battery industry seeks lithium-metal batteries that have improveddimensional stability.

SUMMARY

The embodiments described herein relate to lithium-metal batterieshaving anode cells for reducing dimensional changes during batterycycling. Each anode cell provides an enclosed cavity that contains ananode comprising lithium metal. The enclosed cavity is capable ofaccommodating all expansion and contraction volumes of the anode duringcharging and discharging. Each anode cell also includes a solid-statelithium ion conductor that defines a portion of the enclosed cavity(e.g., a lid). Via the portion, the anode cell is coupledelectrochemically to a cathode cell to form a lithium-metal battery. Inthis coupled configuration, the anode cell separates the anode from anelectrolyte allowing useful formulations of the electrolyte that wouldotherwise react with the anode. Such separation may also prevent aformation of lithium-metal dendrites, which can traverse the electrolyteto form a short-circuit pathway between the anode cell and the cathodecell.

In various lithium-metal batteries, the anode cell includes a containerhaving a first portion and a second portion to form an enclosed cavity.In some variations, the second portion forms one side of the enclosedcavity. The first portion is electrically-conductive andchemically-stable to lithium metal. The second portion is permeable tolithium ions and chemically-stable to lithium metal. The anode cell alsoincludes an anode comprising lithium metal and disposed within thecavity. The anode is in contact with the first portion and the secondportion. The cavity is configured such that volumetric expansion andcontraction of the anode during charging and discharging is accommodatedentirely therein.

The lithium-metal batteries described herein may also be incorporatedinto battery packs. These battery packs include at least onelithium-metal battery having an anode cell electrochemically-coupled toa cathode cell. The anode cell is as described previously and thecathode cell may be any cathode cell that utilizes lithium ions as abasis for electrochemical operation. In some embodiments, the at leastone lithium-metal battery includes a plurality of lithium-metalbatteries arranged in a stacked sequence. The stacked sequencealternates between a first junction formed by adjacent pairs of anodecells and a second junction formed by adjacent pairs of cathode cells.In other embodiments, the at least one lithium-metal battery includes anarray of lithium-metal batteries. In these embodiments, the firstportion of the container for each lithium-metal battery defines asection of an extended first portion shared in common. Otherarrangements of the least one lithium-metal are described for batterypacks.

The lithium-metal batteries may be manufactured using a method thatincludes the step of depositing a seed layer of lithium metal onto asurface of a substrate. The seed layer covers a predetermined area ofthe surface, which matches an orifice of a cavity within anelectrically-conductive container. The substrate includes a solid-statelithium-ion conductor. The method also includes the step of coupling theelectrically-conductive container to the substrate so as to enclose theseed layer within the cavity. Such enclosure includes the seed layerbeing seated within a perimeter of the orifice. The seed layer is incontact with the electrically-conductive container. Other methods ofmanufacturing the lithium-metal batteries are described.

BRIEF DESCRIPTION OF THE DRAWINGS

The disclosure will be readily understood by the following detaileddescription in conjunction with the accompanying drawings, wherein likereference numerals designate like structural elements, and in which:

FIG. 1A is a cross-sectional view of a lithium-metal battery, during acharging process, with an anode cell for reducing dimensional changesduring battery cycling, according to an illustrative embodiment.

FIG. 1B is a cross-sectional view of the lithium-metal battery of FIG.1A, but during a discharging process, according to an illustrativeembodiment.

FIG. 1C is a cross-sectional view of the lithium-metal battery of FIG.1C, but in which the second portion includes a multilayer stack,according to an illustrative embodiment.

FIG. 2A is a schematic diagram of a plurality of lithium-metal batteriesarranged in a stacked sequence, according to an illustrative embodiment.

FIG. 2B is a schematic diagram of the stacked sequence of FIG. 2A, butin which the stacked sequence is electrically coupled in parallel,according to an illustrative embodiment.

FIG. 2C is a schematic diagram of the stacked sequence of FIG. 2A, butin which the stacked sequence is electrically coupled in series,according to an illustrative embodiment.

FIG. 2D is a schematic diagram of the stacked sequence of FIG. 2A, butin which the stacked sequence includes lithium-metal batteries havingaligned polarities, according to an illustrative embodiment.

FIG. 3 is a perspective view of part of an extended first portion havingcavities with corresponding orifices on a common side, according to anillustrative embodiment.

FIG. 4 is a perspective view of part of an extended first portion havinga first planar array of cavities opposite a second planar array ofcavities, according to an illustrative embodiment.

DETAILED DESCRIPTION

Reference will now be made in detail to representative embodimentsillustrated in the accompanying drawings. It should be understood thatthe following descriptions are not intended to limit the embodiments toone preferred embodiment. To the contrary, it is intended to coveralternatives, modifications, and equivalents as can be included withinthe spirit and scope of the described embodiments as defined by theappended claims.

Now referring to FIGS. 1A & 1B, a cross-sectional view is presented of alithium-metal battery 100 having an anode cell 102 for reducingdimensional changes during battery cycling, according to an illustrativeembodiment. FIG. 1A corresponds to the lithium-metal battery 100 duringa charging process and FIG. 1B corresponds to the lithium-metal battery100 during a discharging process. In some embodiments, such as thatshown in FIGS. 1A & 1B, an electrically-conductive portion of the anodecell 102 functions as an anode current collector for the lithium-metalbattery 100. In other embodiments, the anode cell 102 iselectrically-coupled to an anode current collector.

The anode cell 102 includes a container 104 having a first portion 106and a second portion 108 to form an enclosed cavity 110. In theembodiment of FIGS. 1A and 1B, the second portion 108 forms a singlewall of the enclosed cavity 110, and the first portion 106 forms theother walls. The first portion 106 is electrically-conductive andchemically-stable to lithium metal. The second portion 108 is permeableto lithium ions and chemically-stable to lithium metal. In someembodiments, the second portion 108 includes a lid (or serves as a lid)for the first portion 106. In some embodiments, such as that depicted inFIG. 1C, the second portion 108 includes a multilayer stack. In theseembodiments, materials of the multilayer stack and their arrangement maybe chosen so as to avoid a dendritic growth of lithium metal through thesecond portion 108.

The anode cell 102 also includes an anode 112 comprising lithium metaland disposed within the enclosed cavity 110. The anode 112 is in contactwith the first portion 106 and the second portion 108. Such contactallows a flow of electrons (i.e., via the first portion 104) and a masstransport of lithium ions (i.e., via the second portion 108) duringoperation. The enclosed cavity 110 is configured such that volumetricexpansion and contraction of the anode 112 during charging anddischarging is accommodated entirely therein.

The first portion 106 of the container 104 may be formed ofelectrically-conductive material that is non-reactive towards lithiummetal, such as Cu, Ni, Fe, Co, Mn, Cr, V, Mo, W, Nb, and Ta.Alternatively, the first portion 106 may be formed ofelectrically-conductive material having one or more protective coatingsthat are non-reactive towards lithium metal. Such protective coatingsmay themselves be conductive or be applied in areas so that an overallelectrical conductivity of the first portion 106 is maintained. Othertypes of composite configurations are possible for the first portion106.

The enclosed cavity 110 may exhibit various geometries such ascylindrical volumes, rectangular volumes, and hemispherical volumes.Non-symmetrical volumes can also be used. In some embodiments, theenclosed cavity 110 has a cross-sectional area that is constant alongits longitudinal axis 114. In some embodiments, the enclosed cavity 110includes an orifice 116 having a perimeter 118 that defines thecross-sectional area of the enclosed cavity 110. In some embodiments,such as that shown in FIGS. 1A & 1B, the cross-sectional area isconstant along its longitudinal axis 114 and is defined by the perimeter118 of the orifice 116.

As depicted in FIGS. 1A & 1B, the first portion 106 has two enclosedcavities 110 arranged in a “back-to-back” configuration. Thecorresponding orifices 116 face in opposite directions. However, thisdepiction is not intended as limiting. The first portion 106 may haveany number of enclosed cavities 110 arranged in any type ofconfiguration. The orifices 116 may face any direction. For example, andwithout limitation, the orifices 116 may be canted relative to eachother to form patterns (e.g., peaks, valleys, clusters, etc.). Inanother non-limiting example, the orifices 116 may be grouped into rows,each row tilted such that orifices 116 therein face a common direction.It will be appreciated that, for a plurality of enclosed cavities 110,the corresponding volumes may be different in geometry, scale, or anycombination thereof.

The second portion 108 may form a single body with the first portion106, or as shown in FIGS. 1A & 1B, be coupled to the first portion 106as a second body. In some embodiments, the second portion 108 is coupledto the first portion 106 via a seal 120 around the perimeter 118 of theorifice 116. The seal 120 protects a volume within the enclosed cavity110 by excluding contaminants from an environment of the anode cell 102(e.g., an electrolyte). The seal 120 may include a bonding compound thatis chemically-stable with respect to lithium metal, the first portion106, and the second portion 108. In some embodiments, the seal 120includes a copolymer of ethylene and methacrylic acid. The copolymer mayincorporate metal ions such as zinc, sodium, lithium, and potassium.Other additives are possible for the copolymer.

In some embodiments, the second portion 108 may include a solid-statelithium-ion conductor. Non-limiting examples of the solid-statelithium-ion conductor include a lithium phosphorus oxynitride material(e.g., LiPON), a lithium boron oxynitride material (e.g., LiBON), alithium boron oxide material (e.g., LiBO₃), a lithium niobium oxidematerial (e.g., LiNbO₃), a lithium lanthanum zirconium oxide material(e.g., Li₇La₃Zr₂O₁₂), a lithium phosphorus sulfide material (e.g.,Li₃PS₄), a lithium tin sulfide material (e.g., Li₄SnS₄), and a lithiumgermanium phosphorus sulfide material (e.g., Li₁₀GeP₂S₁₂). Othersolid-state lithium-ion conductors are possible. In further embodiments,the solid-state lithium-ion conductor has a lithium-ion conductivitygreater than 10⁻⁷ S/cm. In some embodiments, the second portion 108includes a lithium phosphorus oxynitride material. The lithiumphosphorus oxynitride material may have a stoichiometry ofLi_(x)PO_(y)N_(z) where 3.0≤x≤3.8, 3.0≤y≤4.0, and 0.1≤z≤1.0. The lithiumphosphorus oxynitride material may be amorphous.

In some embodiments, a permeable membrane 122 is disposed along anexterior surface 124 of the second portion 108 and opposite the orifice116. The permeable membrane 122 may extend along the exterior surface124 to portions of the second portion 108 not immediately opposite theorifice 116. The permeable membrane may be any type of permeablemembrane configured to transport lithium-ions therethrough, includingseparators for lithium-ion batteries. In some embodiments, the permeablemembrane 122 exhibits a mean pore diameter less than 0.8 μm.Non-limiting examples of the permeable membrane 122 include polymermembranes of polyethylene (PE) and polypropylene (PP). Such polymermembranes may also include multilayer composites or blends ofpolyethylene (PE) and polypropylene (PP). However, other types ofpermeable membranes and materials can be used.

The anode 112 is preferably pure elemental lithium, but may containincidental impurities less than 2 mole percent. The anode 112 mayoriginate as a seed layer on the second portion 108 when fabricated.When fabricated as the seed layer, the anode 112 has a thickness greaterthan the seal 120, if present, and is fabricated to contact the firstportion 106. FIGS. 1A & 1B depict the anode 112 in corresponding statesof operation different than the as-fabricated state (i.e., not as theseed layer).

During the charging and discharging processes, the anode 112 expands andcontracts in volume. FIG. 1A illustrates the lithium-metal battery 100during the charging process when the anode 112 is plated with lithiummetal to expand in volume. Such plating occurs at the interface with thesecond portion 108. An expansion of the anode 112 is shown in FIG. 1A byarrows 126. FIG. 1B illustrates the lithium-metal battery 100 during thedischarging process when the anode 112 is stripped to contract involume. Such stripping occurs at the interface with the second portion108. A contraction of the anode 112 is shown in FIG. 1B by arrows 128.

The enclosed cavity 110 is configured such that volumetric expansion andcontraction of the anode 112 is accommodated entirely within. Thisconfiguration may utilize a cavity geometry that guides expansion andcontraction along the longitudinal axis 114. The enclosed cavity 110 mayalso be larger than that occupied by the anode 112 at maximum expansion.It will be appreciated that, by accommodating all volumes of the anode112 during charging and discharging, the enclosed cavity 110 can allowouter dimensions of the anode cell 102 to remain virtually constant.

In some embodiments, the enclosed cavity 110 exhibits a vacuum ofmagnitude less than 100 torr. In some embodiments, the enclosed cavity110 exhibits a vacuum of magnitude less than 10 torr. In someembodiments, the enclosed cavity 110 exhibits a vacuum of magnitude lessthan 1 torr. In some embodiments, the enclosed cavity 110 exhibits avacuum of magnitude less than 10⁻¹ torr.

In some embodiments, the enclosed cavity 110 includes a gas disposedtherein. In such embodiments, the gas is inert to reaction with lithiummetal. Non-limiting examples of the gas include helium, neon, argon,krypton, xenon, and combinations thereof. Other inert gases and theircombinations are possible. The gas in the enclosed cavity 110 mayexhibit a reduced pressure of magnitude less than one atmosphere (i.e.,<760 torr).

In various embodiments, the lithium-metal battery 100 includes a cathodecell 130. The cathode cell 130 is electrochemically-coupled to the anodecell 102, which may occur through the permeable membrane 122. Thecathode cell 130 may be any cathode cell that utilizes lithium ions as abasis for electrochemical operation.

In some embodiments, the cathode cell 130 includes a cathode activematerial 132 in contact with the permeable membrane 122 along an area134 opposite the orifice 116. The area 134 may be bounded by theperimeter 118 of the orifice 116, i.e., a projection of the perimeter118 through the permeable membrane 122. Non-limiting examples of thecathode active material 132 include compositions of lithiumtransition-metal (M) oxide such as LiMO₂, LiM₂O₄, and LiMPO₄. M canrepresent Ni, Co, Mn, or any combination thereof. Other compositions,however, are possible for the cathode active material 132.

The cathode cell 130 may also include an electrolyte 136 comprising atleast one solvated lithium species. The at least one solvated lithiumspecies may include a lithium salt. Non-limiting examples of the lithiumsalt include LiPF₆, LiBF₄, LiClO₄, LiSO₃CF₃, LiN(SO₂CF₃)₂, LiBC₄O₈,Li[PF₃(C₂CF₅)₃], and LiC(SO₂CF₃)₃. Other lithium salts are possible,including combinations of lithium salts. The electrolyte 136 permeatesthe cathode active material 132 and the permeable membrane 122 (ifpresent). During operation of the lithium-metal battery 100, theelectrolyte 136 provides a medium through which lithium ions areexchanged between the second portion 108 and the cathode active material132.

The cathode cell 130 may additionally include a cathode currentcollector 138 in contact with the cathode active material 132. Thecathode current collector 138 is formed of an electrically-conductivematerial that is chemically stable to the cathode active material 132and the electrolyte 136. Such chemical stability also includes chemicalstability of the electrolyte 136 towards the cathode current collector138. Non-limiting examples of the electrically-conductive materialinclude aluminum, aluminum alloys, and carbonaceous materials (e.g.,graphite). Other conductive materials, however, are possible. FIGS. 1A &1B depict the cathode current collector 138 as being a foil or sheet.However, this depiction is for purposes of illustration only. Thecurrent collector 138 may exhibit other shapes, including beingintegrated into a housing of the lithium-metal battery 100.

In some embodiments, the electrolyte 136 includes a liquid solvent. Insuch embodiments, the liquid solvent may be an organic carbonate (e.g.,ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl-methylcarbonate, etc.), an ionic liquid (e.g., 1-butyl-3-methylimidazoliumhexafluorophosphate, 1-ethylpyridinium tetrafluoroborate, etc.), or somecombination thereof. Other liquid solvents and their combinations arepossible. In some embodiments, the electrolyte 136 includes a gelpolymer. In these embodiments, the gel polymer may include polymerichosts such as polyethylene oxide (PEO), polyacrylonitrile (PAN),polymethylmethacrylate (PMMA), and polyvinylidene fluoride (PVdF). Othergel polymers are possible.

It will be appreciated that the second portion 108 allows an interfacebetween the anode cell 102 and the cathode cell 130 that separates theanode 112 from the electrolyte 136. Such separation is advantageousgiven that the anode 112 comprises lithium metal. Many usefulformulations of electrolyte 136 are unstable towards lithium metal, andif incorporated within the lithium-metal battery 100 in direct contactwith the anode 112, would decompose during charging and discharging.Separation of the anode 112 from the electrolyte 136 may also prevent aformation of lithium-metal dendrites, which can traverse the electrolyte136 to form a short-circuit pathway between the anode cell 102 and thecathode cell 130 (e.g., between the anode 112 and the cathode currentcollector 138).

In some embodiments, the second portion 108 of the anode cell 102directly contacts the cathode active material 132 of the cathode cell130 (i.e., the permeable membrane 122 depicted in FIGS. 1A-1C is notpresent). In these embodiments, the cathode active material 132 extendsalong the exterior surface 124 to portions of the second portion 108 notimmediately opposite the orifice 116 (e.g., opposite the seal 120). Forexample, and without limitation, the cathode active material 132 mayextend to cover the exterior surface 124 in its entirety.

In operation, the lithium-metal battery 100 undergoes battery cyclingthat involves the charging and discharging processes. During thecharging process, a charging electrical current flows through the firstportion 106 of the container 104 and into the anode 112, which is incontact with the container 104. The charging electrical currentoriginates at the cathode current collector 138 and reaches thecontainer 104 via an electrical circuit (not shown). The chargingelectrical current is provided by an electrical power source, which maybe regulated by the electrical circuit (e.g., to produce controlledvoltage).

The charging electrical current induces positively-charged lithium ionsto migrate from the cathode active material 132, through the permeablemembrane 122 (if present), and to the second portion 108. Such migrationproceeds through the electrolyte 136, which contains the at least onelithium species solvated therein. At the second portion 108, thepositively-charged lithium ions diffuse therethrough to reach the anode112, where they neutralize a negative charge being supplied by thecharging electrical current. This diffusion causes layers of lithiummetal to plate onto the anode 112 at the interface with the secondportion 108. The anode 112 then expands volumetrically within theenclosed cavity 110 (see arrows 126 in FIG. 1A). The enclosed cavity 110is sufficient in shape and size to accommodate the anode 112 at maximumexpansion. The enclosed cavity 110 may include an excess volume as amargin of safety.

During the discharging process, the anode 112 strips at the interface toproduce positively-charged lithium ions. Such mass loss causes the anode112 to contract volumetrically within the enclosed cavity 110 (seearrows 128 in FIG. 1B). The positively-charged lithium ions diffusethrough the second portion 108 where they are solvated by theelectrolyte 136. Transport through the electrolyte 136 allows thepositively-charged lithium ions to reach the cathode active material132, where they are stored therein (e.g., via an intercalation process).In response, a discharging electrical current flows out of the firstportion 106 of the container 104, through the electrical circuit, and tothe cathode current collector 138. The electrical circuit may allow thedischarging electrical current to power an electronic device orelectric-power consuming apparatus. Upon reaching the cathode currentcollector 138, the discharging electrical current flows into the cathodeactive material 132, where it neutralizes the positively-charged lithiumions being stored.

Because all volumes associated with the anode 112 are contained withinthe enclosed cavity 110, outer dimensions of the anode cell 102 remainvirtually constant. Thus, the lithium-metal battery 100 exhibits animproved dimensional stability during operation. Moreover, the secondportion 108 of the container 104 and the seal 120 allow the anode 112 toremain separated from an environment of the anode cell 102, whichincludes separation from the electrolyte 136. Such separation isadvantageous when using formulations of electrolyte 136 that arereactive towards lithium metal. The second portion 108 serves as anionic conductor that mediates chemically between the anode 112 and theelectrolyte 136. In some embodiments, the second portion 108 is assistedby the permeable membrane 122, which resides on the exterior surface 124of the second portion 108 and is exposed to the electrolyte 136.

It will be appreciated that the lithium-metal battery 100 described inrelation to FIGS. 1A-1C can be incorporated into a battery pack. Thebattery pack includes at least one lithium-metal battery 100 having ananode cell 102 electrochemically-coupled to a cathode cell 130. The atleast one lithium-metal battery 100 may be electrically coupled inseries, in parallel, or any combination thereof. In various embodimentsof the battery pack, the at least one lithium-metal battery 100 includesa stacked sequence of lithium-metal batteries 100. In some of theseembodiments, the at least one lithium-metal battery 100 lacks thepermeable membrane 122, i.e., the second portion 108 of the anode cell102 directly contacts the cathode active material 132 of the cathodecell 130.

FIG. 2A presents a schematic diagram of a plurality of lithium-metalbatteries 240 arranged in a stacked sequence, according to anillustrative embodiment. Features analogous to FIGS. 1A-1C and FIG. 2Aare related via coordinated numerals that differ in increment by onehundred. Dashed lines shown a shape of the enclosed cavity 210. Thestacked sequence alternates between a first junction 242 formed byadjacent pairs of anode cells 202 and a second junction 244 formed byadjacent pairs of cathode cells 230.

In some embodiments, the first junction 242 includes a common anodecurrent collector 246 shared between adjacent pairs of anode cells 202,as shown in FIG. 2A. Such sharing may involve a “U-shaped”cross-section. In some embodiments, the first junction 242 includes acontainer wall shared in common between the corresponding first portionsof adjacent pairs of anode cells 202 (e.g., an “H-shaped” cross-sectionin FIGS. 1A-1C). In these embodiments, such sharing may allow thecorresponding first portions to function in combination as a single,extended anode current collector. In some embodiments, the secondjunction 244 includes a common cathode current collector 239 sharedbetween adjacent pairs of cathode cells 230, as shown in FIG. 2A.

It will be appreciated that the common anode current collectors 246 andthe common cathode current collectors 239 can be electrically coupled inparallel, in series, or any combination thereof. FIG. 2B presents thestacked sequence of FIG. 2A, but electrically coupled in parallel,according to an illustrative embodiment. In FIG. 2B, the common anodecurrent collectors 246 are electrically-coupled to an anode bus 248 andthe common cathode current collectors 239 are electrically-coupled to acathode bus 250. The anode bus 248 and the cathode bus 250 maycorrespond to terminals of the battery pack. A voltage potential betweenthe anode bus 248 and the cathode bus 250 may be constant. However,electrical current flowing between the buses 248, 250 scales with anumber of lithium-metal batteries 200 so-coupled.

FIG. 2C presents the stacked sequence of FIG. 2A, but electricallycoupled in series, according to an illustrative embodiment. In FIG. 2C,insulating elements 252 are disposed between cathode current collectors254 and anode current collectors 256 associated with individuallithium-metal batteries 200. The insulating elements 252 preventelectrical current from flowing between adjacent lithium-metal batteries200 (i.e., flowing through the first and second junctions 242, 244).Conducting elements 258 electrically-couple the cathode currentcollectors 254 to the anode current collectors 256 along the stackedsequence. Such coupling allows a potential voltage of the stackedsequence to scale with a number of lithium-metal batteries therein.Electrical current along the stacked sequence may be constant.

A series electrical coupling may also be achieved by altering anarrangement of lithium-metal batteries 200 within the stacked sequence.FIG. 2D presents the stacked sequence of FIG. 2A, but in whichindividual lithium-metal batteries 200 of the stacked sequence havealigned polarities. In this alignment, anode cells 202 and cathode cells230 meet in pairs to form a third junction 260. In some instances, suchas that shown in FIG. 2D, the third junction 260 contains a sharedcurrent collector 262. The shared current collector 262 is stable toelectrochemical processes within the anode cell 202 and the cathode cell230 (e.g., formed of TiAlN or TiAlN-coated stainless steel). In somevariations, the shared current collector 262 includes an anode currentcollector (e.g., copper foil) on one side and a cathode currentcollector (e.g., aluminum foil) on an opposite side. The anode currentcollector and the cathode current collector do not react with each otherduring operation and are inert when the lithium-metal batteries 200 areinactive.

Referring now back to FIGS. 1A-1C, the battery pack may also involvearrays. In various embodiments, the at least one lithium-metal battery100 includes an array of lithium-metal batteries 100. The first portion106 of the container 104 for each lithium-metal battery 100 may define asection of an extended first portion shared in common. Non-limitingexamples of the extended first portion are described below in relationto FIG. 3 and FIG. 4.

FIG. 3 presents a perspective view of part of an extended first portion300 having cavities 302 with corresponding orifices 304 on a commonside, according to an illustrative embodiment. Although the cavities 302are depicted as having a hexagonal cross-section and longitudinal axes306 aligned in parallel, this depiction is not intended as limiting.Other cross-sections and alignments are possible. For example, andwithout limitation, cross-sections for the cavities 302 can includesquare cross-sections, circular cross-sections, and rectangularcross-sections. The cavities 302 may also be canted relative to eachother to form patterns (e.g., peaks, valleys, clusters, etc.). Moreover,the cavities 302 need not be ordered along a hexagonal array, as shownin FIG. 3. Other arrays are possible (e.g., rectangular).

FIG. 4 presents a perspective view of part of an extended first portion400 having a first planar array of cavities 402 opposite a second planararray of cavities 404, according to an illustrative embodiment. Thecorresponding orifices 406 open on opposite sides of the extended firstportion 400. The corresponding cavities 408 are ordered along a square(or rectangular) array. However, it will be understood that the cavities408 of the arrays 402, 404 may be ordered in any type of planar ordering(e.g., hexagonal).

In FIG. 4, the first planar array of cavities 402 is depicted as beingoffset laterally relative to the second planar array of cavities 404.However, this depiction is for purposes of illustration only. Thecavities 408 of each planar array 402, 404 may be aligned such thatcavities 408 on opposite sides share a common longitudinal axis betweenadjacent pairs. The cavities 408 of FIG. 4 are also depicted with acommon square cross-section and longitudinal axes 410 aligned inparallel. However, other cross-sections (e.g., circular, hexagonal,etc.) and alignments (e.g., canted) are possible. These cross-sectionsand alignments may also differ between arrays 402, 404 and betweenindividual cavities 408 within an array.

Now referring back to FIGS. 1A-1C, in embodiments involving the extendedfirst portion, the array of lithium-metal batteries 100 may be orientedsuch that the corresponding enclosed cavities 110 have orifices 116 on acommon side of the extended first portion (e.g., analogous to FIG. 3).In these instances, the corresponding cathode cells 130 may beconfigured into a single, effective cathode cell that spans the extendedfirst portion. Such configuration may include the cathode activematerial 132 and the cathode current collector 138 as single respectivelayers that extend to limits of the extended first portion. The secondportion 108 and the permeable membrane 122 may also be single respectivelayers that extend to limits of the extended first portion. Thus, thearray of lithium-metal batteries 100 may include a single cathode cellthat is shared in common among a plurality of anode cells 102.

The array of lithium-metal batteries 100 may also include a first planararray of lithium-metal batteries 100 opposite a second planar array oflithium-metal batteries 100. The corresponding enclosed cavities 110 areoriented such that their orifices 116 open on opposite sides of theextended first portion (e.g., analogous to FIG. 4). In such instances,the cathode cells 130 associated with each side may be configured into asingle, effective cathode cell. Thus, the array of lithium-metalbatteries 100 may include a single cathode cell on each side of theextended first portion. The single cathode cell may extend to limits ofthe extended first portion and may be shared in common among anode cells102 on one side. The second portion 108 and the permeable membrane 122may also be configured as single respective layers that extend to limitsof the extended first portion on one or both sides.

The anode cells, the lithium-metal batteries, and the battery packsdescribed herein can be used in any device that requires rechargeable ornon-rechargeable batteries. In some variations, the anode cells,lithium-metal batteries, and the battery packs described herein can bepackaged in to an apparatus that is battery-powered.

According to an illustrative embodiment, a method of manufacturing alithium-metal battery includes the step of depositing a seed layer oflithium metal onto a surface of a substrate (e.g., by vacuum deposition,electroplating, etc.). The seed layer covers a predetermined area of thesurface, which matches an orifice of a cavity within anelectrically-conductive container. The substrate includes a solid-statelithium-ion conductor. The method also includes the step of coupling theelectrically-conductive container to the substrate so as to enclose theseed layer within the cavity. Such enclosure includes the seed layerbeing seated within a perimeter of the orifice. The seed layer is incontact with the electrically-conductive container. In some embodiments,the step of coupling the electrically-conductive container to thesubstrate includes sealing the electrically-conductive container to thesubstrate.

It will be appreciated that the perimeter of the orifice matches that ofthe predetermined area. Thus, the seed layer, when enclosed within thecavity, has a boundary that aligns with the perimeter of the orifice.This alignment allows the seed layer to be in contact with theelectrically-conductive container. In some embodiments, theelectrically-conductive container is coupled to the substrate via aseal. The seal may be a hermetic seal. In these embodiments, the seedlayer has a minimum thickness that is greater than a distance separatingthe electrically-conductive container from the substrate (e.g., a sealthickness). The minimum thickness may prevent a gap between the seedlayer and the electrically-conductive container.

Non-limiting examples of the solid-state lithium-ion conductor include alithium phosphorus oxynitride material (e.g., LiPON), a lithium boronoxynitirde material (e.g. LiBON), a lithium boron oxide material (e.g.,LiBO₃), a lithium niobium oxide material (e.g., LiNbO₃), a lithiumlanthanum zirconium oxide material (e.g., Li₇La₃Zr₂O₁₂), a lithiumphosphorus sulfide material (e.g., Li₃PS₄), a lithium tin sulfidematerial (e.g., Li₄SnS₄), and a lithium germanium phosphorus sulfidematerial (e.g., Li₁₀GeP₂S₁₂). Other solid-state lithium-ion conductorsare possible. In some embodiments, the solid-state ionic conductor has alithium-ion conductivity greater than 10⁻⁷ S/cm. In some embodiments,the solid-state ionic conductor includes a lithium phosphorus oxynitridematerial. The lithium phosphorus oxynitride material may have astoichiometry of Li_(x)PO_(y)N_(z) where 3.0≤x≤3.8, 3.0≤y≤4.0, and0.1≤z≤1.0. The lithium phosphorus oxynitride material may be amorphous.

In some embodiments, the method further includes the step of depositingthe solid-state lithium-ion conductor on a removable support (e.g., byvacuum deposition, electroplating, etc.). The removable support can beremoved from the solid-state lithium-ion conductor before or after thesubstrate is coupled to electrically-conductive container. In someinstances, the removable support is detached physically from thesolid-state lithium-ion conductor. In other instances, the removablesupport is removed from the solid-state lithium-ion conductor throughone or more sacrificial processes (e.g., dissolving in a solvent,melting, heating to decompose, etc.).

In some embodiments, the step of depositing the seed layer of lithiummetal includes the step of depositing the solid-state lithium-ionconductor onto a cathode active material (e.g., by vacuum deposition,heat-molding, etc.). In these embodiments, the cathode active materialmay be configured as part of a cathode cell.

In some embodiments, the step of depositing the seed layer of lithiummetal includes the step of depositing the solid-state lithium-ionconductor onto a permeable membrane having a first surface and a secondsurface. In these embodiments, the first surface forms an interface withthe solid-state lithium-ion conductor. An exposed surface of thesolid-state lithium-ion conductor defines the first side of thesubstrate. The substrate further includes the permeable membrane.

The permeable membrane may be any type of permeable membrane configuredto transport lithium-ions therethrough, including separators forlithium-ion batteries. In some embodiments, the permeable membraneexhibits a mean pore diameter less than 0.8 μm. Non-limiting examples ofthe permeable membrane include polymer membranes of polyethylene (PE)and polypropylene (PP). Such polymer membranes may also includemultilayer composites or blends of polyethylene (PE) and polypropylene(PP). However, other types of permeable membranes and materials can beused.

In some embodiments, the step of depositing the solid-state lithium-ionconductor onto the permeable membrane includes the step of contacting acathode active material with a cathode current collector to produce apreform. In such embodiments, the step of depositing the solid-statelithium-ion conductor onto the permeable membrane also includes the stepof contacting the cathode active material of the preform with the secondsurface of the permeable membrane and the step of applying heat,pressure, or a combination thereof, to the preform in contact with thepermeable membrane. The substrate further includes the cathode activematerial and the cathode current collector.

Non-limiting examples of the cathode active material includecompositions of lithium transition-metal (M) oxide such as LiMO₂,LiM₂O₄, and LiMPO₄. M can represent Ni, Co, Mn, or any combinationthereof. Other compositions, however, are possible for the cathodeactive material. The cathode current collector may be formed of anelectrically-conductive material such as aluminum, aluminum alloys, andcarbonaceous materials (e.g., graphite). Other electrically-conductivematerials, however, are possible. The cathode current collector may be afoil or sheet.

In some embodiments, the step of coupling the electrically-conductivecontainer to the substrate includes the step of coupling an anodeterminal to the electrically-conductive container and the step ofcoupling the cathode terminal to the cathode current collector. Infurther embodiments, the step of coupling the electrically-conductivecontainer to the substrate includes the step of disposing, into a pouch,the electrically-conductive container coupled to the substrate; the stepof filling the pouch with an electrolyte; and the step of sealing thepouch.

The anode terminal may be formed of any electrically-conductive materialchemically compatible with the electrically-conductive material.Similarly, the cathode terminal may be formed of anyelectrically-conductive material chemically compatible with the cathodecurrent collector.

The electrolyte includes at least one solvated lithium species. The atleast one solvated lithium species may include a lithium salt.Non-limiting examples of the lithium salt include LiPF₆, LiBF₄, LiClO₄,LiSO₃CF₃, LiN(SO₂CF₃)₂, LiBC₄O₈, Li[PF₃(C₂CF₅)₃], and LiC(SO₂CF₃)₃.Other lithium salts are possible, including combinations of lithiumsalts. The electrolyte may permeate the cathode active material and thepermeable membrane (if present). The electrolyte may also include aliquid solvent. The liquid solvent may be an organic carbonate (e.g.,ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl-methylcarbonate, etc.), an ionic liquid (e.g., 1-butyl-3-methylimidazoliumhexafluorophosphate, 1-ethylpyridinium tetrafluoroborate, etc.), or somecombination thereof. Other liquid solvents and their combinations arepossible. In some embodiments, the electrolyte includes a gel polymer.In these embodiments, the gel polymer may include polymeric hosts suchas polyethylene oxide (PEO), polyacrylonitrile (PAN),polymethylmethacrylate (PMMA), and polyvinylidene fluoride (PVdF). Othergel polymers are possible.

The foregoing description, for purposes of explanation, used specificnomenclature to provide a thorough understanding of the describedembodiments. However, it will be apparent to one skilled in the art thatthe specific details are not required in order to practice the describedembodiments. Thus, the foregoing descriptions of the specificembodiments described herein are presented for purposes of illustrationand description. They are not targeted to be exhaustive or to limit theembodiments to the precise forms disclosed. It will be apparent to oneof ordinary skill in the art that many modifications and variations arepossible in view of the above teachings.

What is claimed is:
 1. An anode cell for a lithium-metal battery, theanode cell comprising: a container having a first portion and a secondportion to form an enclosed cavity, the first portionelectrically-conductive and chemically-stable to lithium metal, thesecond portion permeable to lithium ions and chemically-stable tolithium metal; an anode comprising lithium metal and disposed within theenclosed cavity, the anode in contact with the first portion and thesecond portion; wherein the enclosed cavity is configured such thatvolumetric expansion and contraction of the anode during charging anddischarging is accommodated entirely therein; wherein a volume of theenclosed cavity is larger in size than a volume of the anode disposedtherein; wherein the second portion separates the anode from anelectrolyte disposed external to the enclosed cavity; wherein theelectrolyte comprises a lithium salt; and wherein the second portiondirectly contacts the anode.
 2. The anode cell of claim 1, wherein thesecond portion comprises a lid for the first portion.
 3. The anode cellof claim 1, wherein the second portion comprises a multilayer stack. 4.The anode cell of claim 1, wherein the enclosed cavity has across-sectional area that is constant along a longitudinal axis thereof.5. The anode cell of claim 4, wherein the enclosed cavity comprises anorifice having a perimeter that defines the cross-sectional area.
 6. Theanode cell of claim 5, further comprising a permeable membrane disposedalong an exterior surface of the second portion and opposite theorifice.
 7. The anode cell of claim 5, wherein the second portion iscoupled to the first portion via a seal around the perimeter of theorifice.
 8. A battery pack, comprising: at least one lithium-metalbattery having an anode cell electrochemically coupled to a cathodecell, the anode cell comprising: a container having a first portion anda second portion to form an enclosed cavity, the first portionelectrically-conductive and chemically-stable to lithium metal, thesecond portion permeable to lithium ions and chemically-stable tolithium metal, an anode comprising lithium metal and disposed within theenclosed cavity, the anode in contact with the first portion and thesecond portion, wherein the enclosed cavity is configured such thatvolumetric expansion and contraction of the anode during charging anddischarging is accommodated entirely therein; wherein a volume of theenclosed cavity is larger in size than a volume of the anode disposedtherein; wherein the second portion separates the anode from anelectrolyte disposed external to the enclosed cavity; wherein theelectrolyte comprises a lithium salt; and wherein the second portiondirectly contacts the anode.
 9. The battery pack of claim 8, wherein theenclosed cavity comprises an orifice having a perimeter; and wherein theanode cell further comprises a permeable membrane disposed along anexterior surface of the second portion and opposite the orifice.
 10. Thebattery pack of claim 9, wherein the second portion of the container iscoupled to the first portion of the container via a seal around theperimeter of the orifice.
 11. The battery pack of claim 9, wherein thecathode cell comprises: a cathode active material in contact with thepermeable membrane along an area opposite the orifice; an electrolytecomprising at least one solvated lithium species; and a cathode currentcollector in contact with the cathode active material.
 12. The batterypack of claim 8, wherein the at least one lithium-metal batterycomprises a plurality of lithium-metal batteries arranged in a stackedsequence; and wherein the stacked sequence alternates between a firstjunction formed by adjacent pairs of anode cells and a second junctionformed by adjacent pairs of cathode cells.
 13. The battery pack of claim12, wherein the at least one lithium-metal battery comprises theplurality of lithium-metal batteries arranged in the stacked sequence;and wherein individual lithium-metal batteries within the stackedsequence have aligned polarities.
 14. The battery pack of claim 8,wherein the at least one lithium-metal battery comprises an array oflithium-metal batteries; and wherein the first portion of the containerfor each lithium-metal battery defines a section of an extended firstportion shared in common.
 15. The anode cell of claim 1, wherein thelithium salt comprises at least one of LiPF₆, LiBF₄, LiClO₄, LiSO₃CF₃,LiN(SO₂CF₃)₂, LiBC₄O₈, Li[PF₃(C₂CF₅)₃], and LiC(SO₂CF₃)₃.
 16. The anodecell of claim 1, wherein the second portion comprises at least one of alithium phosphorus oxynitride material, a lithium boron oxynitridematerial, a lithium boron oxide material, a lithium niobium oxidematerial, a lithium lanthanum zirconium oxide material, a lithiumphosphorus sulfide material, a lithium tin sulfide material, and alithium germanium phosphorus sulfide material.
 17. The battery pack ofclaim 8, wherein the lithium salt comprises at least one of LiPF₆,LiBF₄, LiClO₄, LiSO₃CF₃, LiN(SO₂CF₃)₂, LiBC₄O₈, Li[PF₃(C₂CF₅)₃], andLiC(SO₂CF₃)₃.
 18. The battery pack of claim 8, wherein the secondportion comprises at least one of a lithium phosphorus oxynitridematerial, a lithium boron oxynitride material, a lithium boron oxidematerial, a lithium niobium oxide material, a lithium lanthanumzirconium oxide material, a lithium phosphorus sulfide material, alithium tin sulfide material, and a lithium germanium phosphorus sulfidematerial.